Process involving exchange reactions



May 29; 1928 I 1,671,864 E. B. HIGGINS PROCESS INVOLVING EXCHANGE REACTIONS Filed Sept.24, 1925 5 Sheets-Sheet l 9/ *2 Fig.1.

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Am/vers May 29, 1928. 1,671,864

E. B. HIGGINS .PROCESS INVOLVING EXCHANGE REACTIONS Filed Spt. 24, 1925 5 Sheets-Sheet 2 May 29,1928. 1,671 ,864

E. B. HIGGINS PROCESS INVOLVING EXCHANGE REACTIONS Filed Sept. 2 1925 s Sheets-Sheet 5 5y w A RIVEY6 M a129, 1928. p

UNITED STATES PATENT OFFICE- i mo HIGGINS, 01' LONDON, ENGLAND, ABS 16x03 LIMITED, LOKDONI, ENG

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P3OCEBS INVQLVIIt'G EXCHANGE BEAGl'IOHS.

Application fled September :4, 1925, Serial lo. 58,845, and in Great email we, 1,

This invention relates to processes involving exchange reactions, that is to 'say, reactions in which an exchange material is employed to take up a substance and, subsequently, by'a reversal, is restored toits active conditionby a process usually known asregenration. Anjexample of such a reaction to whichthe present invention has particular reference is the softening of water by base exchange materials. Such reactions are considered to be true chemicalreactions or to depend upon adsorption or to have the characteristics of both according to the conditions under which the process is carried Generally speaking the exchange material, for. example the water sot.-

teningmaterial, has hitherto been employed 1n practice inthe form of; af' filter bed, the integrity -of: which has been --ma1n'ta1ned durihgfthe'process. -'-The"'suggestion has,

however, been made to workwith the-material in suspension in-the water, but. such suggestion has "not matured into practical use. There are: certain drawbacks, however, inherent in the method of. using exchange material in theform of a filter b'cd.-- 'First of all the process cannot be truly continu- 0115 because the'softening reaction has to be stopped after a certain period, and the exno change material has to regenerated to be rendered fullyactivie again. Again, particles of theexchange material which are finer :than'a' certain grade cannot be employed-in 'a filter as, they tend' to form a mud which would quickly fill up the intersticesand choke the filter bed. Thus, for

this reasonthere is a considerable waste of I n'iaterial, such as glauconite, which cannot water softening owing to the finenelnz' of its constituent particles; Again,

with relatively coarse particles lying in a filter bed, there is such an amount of contact that substantial parts of the surfaces of the particles, which might be active and take part i'n'the reaction, are prevented [from doing so asthey cannot come into contact with the water.

It is recognized that in order to: promote adsorption it is more important to increase the surface of the exchange material than itis to increase the time of the reaction. ;-The chief objects of the present invention then are to enable such exchange reactions to be carried out in such a manner that the free active surface of the exchange body is inmaf creased as much as possible,to enable the reducing the amount. of exchange material necessary to deal with a given amount of the material to be treated. 7

According to the present invention the elfrchange material is maintained ina state 0 liquid taking part in the reaction, being caused to flow upwar that is to sayagainst the natural direction of fall of thd exchange material. In the case of Water softening, the exchange material be maintained in a state of suspension by the upwardly flowing hard water, or it may be maintained in suspension during the regeneration process by the upward flow of the regenerating solution, usually common 30' salt, or, of course, both parts of the process maybe carried out while the exchange material is maintained-in a state of suspension due to the upward flow of the respective liquids. By the present invention the net rate of'fall ofthe exchange material is the difference between its natural speed of fall and the upward velocity of the liquid quest ion'. The three cases which may arise in practice are as follows: If the upward velocity of theliquid is equal to the natural rate of fall of the exchange material, the actual rate of fall becomes zero, and in theory the exchange material remains stationciently nearly approached in practice,,although it isv actually impossible to produce a flow of the liquid to be treated or of the regenerating liquid free from eddy currents. Secondly, be at a velocity which is greater than ,the natural rate of fall of the exchange material. The actual rate 'of fall is negative,- that is to say, the material moves u wardlyin space at a velocity equal to the difierenoe 105 between the upward speed of the liquid and the natural rate of fall of the exch'an e material. Finally, the rate of upward ow of the liquid may be less than the. natural rate of tall of the exchange material, and then no in truly continuous suspension during the reaction by the may thus ary in space, and this condition can be sufiias the upward flow of the watermay 10o for examplev in the case of water so the latter an falls at; which is less than its natural rate of fa i, being equalto the "difierenoe between its natural rateof "fall .and the upwardvelocity of the liquid.

The time of contact between the exchang: material and the liquid, as a whole to treated, or there eneratin liquid, can be into contact with the regenerating liquid.

In order that the invention may be clearly understood and readily carried into efiect, some examples of processes according to the invention, particularly as ap lied to water softening, will be described in detail with reference to the accompanying diagrammatic drawings, where1n: A

Figure 1 is a diagrammatic elevation of one form of apparatus in which the present invention may be carried out;

Figure 2 is a similar view showing a somewhat modified form of apparatus;'

Figure 3 is again-a similar view showing a somewhat further modified form of app w Figure 4 is, again a similar view showing adevelopment of the apparatus illustrated in Figure 2, by means of which the process can be brought nearer to a complete cycle; Figure 51s a. similar view showing-a further form of apparatus wherein the net movement of the exchange material in space is u 'ward; lgure 6 is a similar view showing an a aratus whereinmorc than one form oft e invention is used at different parts of the. cycle; and

Figure 7 isa section showing a detail. In Figures 1 to 4 forms of apparatus are illustrated suitable for carrying out the of the liquid column is as'ncar as is process in such a way that the upward speed rac-' ticable equal to' the natural rate'of fa ll of the exchange material.

ferrmgfirst of all to Figure 1, ajvessel 1 is employed, the crdss-sectional area of which increases continuously' from the bottold upwardyin other-words, the vessel 1 is in the form of a truncated cone with its vertex downward. l particular example may be considered wherein the base exchange material, for example glauconite,.which has been stabilized, for example, by

pii-iferably V been graded by elutriatioii or otherwise ;so that none or it-sparticles will ...move upwards in a stream of water moving L-' at ;-a,1inearvelocity of"2.5 centimeters per second, and willnot fall a'gainst a streamof suflicient salt will have cute '13 parts lime water moving at 15 centimeters -persecond.

hard water may flow in by the pipe 2, and- 10% common salt solut-ionfor regenerating This corresponds roughly with the glauconite 7 wherein the iprarticles Wlll pass a sieve of 40 purposes may flow in by the pipe 3. The

pipe 2 has a stop valve 4, and the pipe 3 a stop valve 5, so that either or both'o these sup lies may be entirely shut 01!. The rate of ow of either of them u wardly through the vemel 1 is-controlled y -a regulating.

valve 6 and in the example underconsidera; tion it may be assumed. that the valve 6 is set so that water or salt sol'ution mayflow' through the apparatus at a rate of 2 gallons per minute. a

Under these the vessel 1, atits upper edge at 7, maybe 3 inches, giving a cross-sectional area corresponding to alinear velocity over the area of 2.5 centimeters per second. at the rate of flow of the liquids mentioned above.

Again,the diameter of thevemel 1, at its lower end at 8, may be 2 inches, which is calculatedto givef a cross-sectional area corresponding to a linear velocity over the area of 5. centimeters per second with the rate of flow of the liquids mentioned above. The height of the vessel 1, between the points 7 an 8, may be 6 feet, and the vesse isprovided with an expansion 9 at its upper end,

which. may be 8 inches-high from the point 7' to its .up r edge, and maybe 12 inches in efiective iameter. The expansion 9 is-provided with an outflow pipe 10-.

' he followin cycle of operation'smay be e rformed in t is 'ap aratus. The valve 4 1s closed' and the va ve 5 opened, for example for 30 seoonds,.durin which time to re nerate the material,-and then water allow to flow first'to waste. by opening the valve 4 and shutting the valve 5 for say 3 minutes. Thisserves to wash out thebrine from the glauconite in the vessel 1. The latter ma contain approximately 8 kilogrammes 0 base exchange materia The water, after 3 minutes, is allowed. to a storage tank at will, and it will found that'the conditions the diameter of I exchange material can soften water at, the high rateof 116wmentioned above, which is equal to an average metric flow of 135 meters per hour. u deliver, for example witha hard water of r 100,0), 28 to 30 gallons of soft water stay, that is to say, in. approximately 15 minutes. grade of base exchange ma-- terial-be employed, for example one in which- If'a coarser none: of its particles will moveupwards in a stream of water movin centimeters per second, an no particle will ch; an apparatus will fore regeneration is neces at 7 be not less Y an that I ticular conditions. If the 'diameter at the not rise quite-to the change material having a greaterfliversity in the dimensions of where otherwise the same referen merals have been applied as in Figure 7 shall be coned all against a water streamjlowing upwards at10 centimeters per second,-theonly alteration. in the apparatus described above that is necessary would beto change the diameters a't the-points '1 and. 8'to respectively 3 inches and-2% inches. Such an apparatus would act as before except that its rate of softening would be equivalent to a they are obvious and, ofcourse, form no part of the present invention. A

It is, of course, not necessary that the diameter specified at the int? should actual- 1y be at the top, rovirlzl that the diameter specified for partop is greater, it merely means that the base exchange material, du operation, will as? the-vessel 1.- v Furthermore, it is" clear that bases-texthe ains and in vtheir natural rates of all may em ldyedifthe taper of the conical vessel 1 mcreased,"

Such an example is illustrated. in 2,

is only necessary that-the liquid supply be fed at such a rate that at some the velocity shall be greater than that at which the largest particle of the base ex-' change material can fall, and that'at some other point 7 the velocity shall be such that the smallest particle of the base exchange. material shall sink. 1 ,s

- It is also ry that the vessel 1 entire length. vessel 1 is cylindrical in form, and the expansion 9 isjoined to the vesel 1b a coni-r cal portion 11,-and the vessel 1 is'joined to P the supply pipe 12 by a furtherconicalpor tion 13. Thediameters are such that-the upward velocity 'ofthe liquid in the vessel in the part 13 isgreater than therein, while the rate of fall of .1 is less than the rate at which the base exchange material rises irsthe liquid thesvelocityof the liquid in the expansio 9 is such that thematerial falls in ter the liquid the natural ".rateof fallofthe. coarsest particle of exchange material. all

referred p mt 8- orftapered uniformly overitsl aFor example,in Figure 3 the"- change material is carried beyond a certain part .13 but cannot vrise above,

level inthe the tapered portion 11, and the majorityof it isretained in the vessel-1. For example, with the grade of base-exchange material toin the firstexample 'ven above, the velocity of flow of the liq 13 must'be above 5 centimeters per second,

and the rate of flow in the part9 must be below 2.5.centimeters per second, the rate of flow in the vessel 1 beingbetween these two values.

in the part In-the modified form ofthe a 'paratus shown in 'Figure4 the main part 0 the apparatus comprises a container 1 and anexpansion 9' with an outflow 10 substan-- P tially the s ameas-shown in 1 and y 2. Below the vessel 1, however, there are c a pair of receivers 14, 15, the diameter of each of which is less than the diameter of the vessel 1 atthe throatS. The receivers 14, 15 are in connection withthe vessel 1 through valves 16, 17, and the hard water is introduced to one or other of the vessels 14, 15 alternately through regulating valves 6 and 6" from-the ipe 12. Clearly, if the stream of water be disconnected entirely, the

base exchange material in the container 1 will fall, due to'its own weight, out of the container into one or other of the receivers #14, 15, according to whichvalve 16 or 17 15 open, and then by closing the appropriate valve the material may be isolated in the receiver 14or15, which it.fills,

and may e there regenerated or otherwise treated. The

receivers 14, '15 are connected to the drain Insoften ng water by the apparatus shown in Figure 4, thewater may be admitted througthe valve 6", receiver 15, valve'17, will so ned in the vessel 1, and the soft water will-flowout through the pipe 10.

The rate of flow of the water is such as to maintain the base exchange material above the throat 8 during the reaction. "When the l a through valves 18, 19, and to asupply of a regenerating solution through valves 26, 21.

inaterialis exhausted the valve 6 is shut ofi,

the materiahimmediately; falls into the receiver 15; Thamh valve 17 is; closed and the valve 6' andZ-lfligpened, when another char ofbase material exchan previously ntfthe-receiver 14 1s swept up into the container 1 and softening goes on again.- In the meantime, sal solution 1sadmitted at 21, regenerates the material inthe receiver "15, and flows out at 19. Then the valve 21- is closed, and water admitted r through the valve. 6" to washout; the brine intheha'seexchange material'in the vesel 15, and then flows-out to waste at "19. The regenerated char-gs" in --the receiver 15' is readyto mtogthe container-1 when cl-ge at preaent therein has dropped '14, Thus; the softening and regenerating processes. can be carried out nearl in a continuous cycle in the apparatus s own in'Figure 4.

As already mentioned, Figure illustrates an apparatus wherein the process may be carried out in a column in which the up ward velocity of the li uid is at all points greater than the natura rate of fall of the largest particle contained in the'exchange material. The base exchange materialvis contained in a vessel22 and is there in the active or regenerated condition. The treating vessel 1 is a pipe-shown. of uniform crosssectional area, although it may increase-1n cross-sectional area towards the bottom or the top, depending u '1 n whether uniform velocity throughout t e column is desired, or a decrease in velocity, or an increase in velocity. The water to be softened is admitted from a pipe 12' and passes through an injector 13, flowing into a pipe 23 and carrying with it. a quantity of the base ex-. change material from the vessel 22. The water flows into the treating vessel 1 and when it leaves this vessel 'atthe top, an runs over with the base exchange material into the receiver 24, it has become entirely softened, and base exchange material collects in the receiver 24, and the softened as shown in t tedjn F gures 6 and 7 ma .water flows outb thepipe 25. As an example of the con itions in which the necessary softening can be e constituting the treating vessel, it maybe mentioned that the pipe 1 may have a diameter of 2 inches and a height of 9 feet from the point of entry of the inlet of the injector 13 to the top of thepipe 1. .The

.water issupplied. through the pipe 12 at a rate of 1.62 gallons-per minute, and the injector is designed'so that in the'pi 1 one volume of base exchange materia passes for every four volumes of water, the base exchange material being glauconite graded as in the first exam ledisoussed so that the natural rates of fa l-of its particle liebeger'second. It-

zero hardness with a'mean metric flow of 217 meters per hour.

As already mentioned, the apparatus illuses use of the combination of more than one of the methods already indicated, It will be seen that different methods are. employed in difierent flected in the pipel,

way of t is height is poses which takes igure 5, will deliver water of I 'ously in the v 31, slowly in the upper:

parts of the treating apparatust {In Figure 6,

the base exchange material',' which ma be- If the considered to be glaucenite*in .-:-which a particles have a natural rate of fall between 2.5 and 5 centimeters per. second, is placed in the active or-regenerated condition in the vessel 22, and exactly as in the system shown in Figure 5 'is drawn into the treati v vessel or pipe 1 by the hard water admitted t rough the pipe 12, and flowing through the injector 13. It may be assumed as before that the flow of water is regulated by the-valve 6 at a rate of 1.6 gallons per minute, and that I one volume of the above base excha e material is taken into the pipe 1' wit four volumes of the hard water. Again, the pipe 1 may be 2 inches in internaldiameter, and its height from the point26 to'the top at 27' is 12 feet. e pipe 1 extends into an expanded vessel 9 which may be one foot six inches in diameter and may be 2 feet in height from the point 28, to the top. The point 28 may be one foot below the point 27 so that the. pipe 1 extends for one foot into the expanded vessel 9. 10 is the outflow for the soft water, as previously. The water,

by the time it has reached'the point 27 underthe conditions just described, has attained zero hardness, and flows together with the base exchange material indicated at 29 into the expanded vessel 9, and thence through the outflow pi '10. The base exchange material slowly flzws out through a gate valve -30. This .is'. shown somewhat in detail in Figure 7 where 9' and 9" indicate the wall of the expanded vessel 9 on either side of the outletaperture, the walls being cham-.

fered inwards, as shown, and the sliding gate valve 30 is also chamfered, as shown, at its lower edge to produce a minimum resistance to the outflow of the wet glauconite. Withoutsome such arrangement, the glauconite cannotbe made toflow out through the valve. 1

The glauconite drops into a further liquid column in a regeneratin and washing vessel 31, the diameter of w ich may be, in the example chosen, 1 inches. .The height of the vessel 31 from the top of the vessel 22 to its up rmost edge may be 8 feet. Midcommon salt solution for regenerating purlace through the valve 5. The water for was ing out the salt from the regenerated material enters through a valve 32, the rate of 'flow of'the washing water beingaboutthe same as that of the salt. andv approximately at 10 gallons per hour.. Thus, t e upward linear flow of the washing water in the lower part of the vessel 31 is 1 centimeter per second, and the upward flow of the mixed salt and washing water in the upper part of the vemel 31 is about 2 linear centimeters per second. Thus, the exhausted base exchange material will sink continuthe inlet for the 10% 1 but more turns to th I cannot such processes. It is also applicable to other quickly in the lower half, andree vessel -22, keeping the latter substantiall filled so that the rinsing water tlhw back around the injector 13. It has been found that an apparatus of the dimensions indicated will soften water from' 13 degrees of hardness to zero hardness at the rate mentioned of 1.6 gallons per minute, which is equivalent to a metric flow of 217 meters per hour.

Although" the invention has been described in the particular examples in connection with its application to water softening and to the regeneration of the exchange material, it must be understood that it is not limited to cases wherein reversible adsorption takes place. For example, a known method for removing iron in solution from water consists inemploying a zeolite or equivalent body substantially acting as a vehicle for the higher oxides of manganese. Very considerable difiiculties are encountered in a filter of this material as the iron oxide liberated from the water clings to the grains of. the manganese'zeolite and quickly chokes-the filter. If such a man "anese zeolite is employed, for example in t e apparatus illustrated in Fi ure 1, the reaction goes on perfectly. The particles of the exchange-material are con stantly in gentle-agitation and, apparently as a result of this, the iron oxideis rubbed off the surface of the grains, and being extr'emely light, is merely carried awa by the rising water flowing over the top- 0 the apparatus, and can be readily separated b fil tration. The invention is also particu arly applicable tocases in which reversible polar orption takes place; for exampleit may be applied where the exchange material is orptive such as blood-charcoal, the

queous solution such as a solution of'picric acid, and the regenerati agent is a less active solvent such as ethy "alcohol. Also, theinvention may be applied to processes involving the reversible a sorption bf radio active materials such'as uraniumXJ by charcoal from aqueous solutel-s Patent is:-

Having thus descrihed my reaction which consists exchange material in a tion wherein solutions of thorium salts and so forth are employed as the regenerating agent. invention, what I c as new and desire to secure by Let- 1. A process for carrying out an exchange 'in maintaining the' state of suspension in a liquid to be treated untilthe exchange reaction has been substantially completed b means of the upward flow of the said liquid:

2. A process for carout an exchange liquid which consists in maintaini ward flow of the said li uid that at points the Speed is equal ifierent to the natural totes depending u n the ex :to the action in a container and liquid, supplying the by base .exchan 'taining the herd and the of fallof the di'fi'erent change material in the li ing ultimately altered w remove the exchange material from the treating vessel. 7

A process for carrying out an exchange reaction between an'exchange material and a liquid which consists in maintaining a linear speed of upward flow of the li uid greater t an the natural rate of fall in t e liquid of the coarsest'particles of the exchange material, so that the latter travels upwards at a lower speed than that of the liquid-and'the exchange reaction is completed while the liquid is-t'raveling'uflwards in contact with the exchange materla I 4. A process for the softening of water by base exchange which consists inmaintaining the exchange mater al in a state of suspension in an upward flowing column of hard water which consists in maintainin the rate of flow of the hard water at such a speed that the exchange material is maintained in suspension for a period long enough for the exchange reaction to bejsubstantially completed.

-5. A process for ca.

' ange of bases conan exchange material of an upward current of liquid causing said liquid to ow upwardly at a linear 'velocit creases as the liquid rises so at there are zones in the .li 1nd of rogressivelydecreasing linear epochs, which latter are such that there is a linear rate of fall in the liquid of the particles of said exchange'material of each different size. 6. A process for carrying; out an exchange reaction between an. exchange material n granular form and aliquid, which consists in maintaini sisting m an mitting speed equal to the natural ing out a reaction which dean upward flow'of the said granular material to said liquid and re ulatmg the linear speeds 7 of the liquid at e'footof the column of flow and at the head of the the coarsest particles of the exchange .terial will not sink ,to the'bottoin and the finest particles not escape over the flip.

A process. for the softening of water which consistsinmainupwardly flowing column, ceding a quan tity of zeolite-like heat; exchange material to said column and regu' let the linears the water at t hg footof the c ib l umn at the head of the column sothat the, coarsest rticles ofthe zeolite-like body will not s' the top.

column so that water to be trea ed ini to the bottoniofthe column finestparticleswill not over 8. A process'for the softening of water by. a

an uphas: exchange which consists in an upward current of hard waterm a contnnertotheectioaofheee terial in the granular form, causing the water which decreases as the liquid rises, aupplyto flow upwardly at a linear velocity which ing th oase exchange material to said coldecreases as the water rises, so that there umn, the varying linear velocity of the water 20 are zones in the current of liquid moving at being such that there are zones in the col- 5 progressively decreasing linear speeds, unin of linear speeds just sufiicientto mainwhich latter are such that there is a linear tain in suspension the particles of the exspeed equal to the natural rate of ran in the change material of each difierent size, subwater of the particles of each different size seqnently causing the base exchange material 25 of said exchange material so that said exas it approaches exhaustion to leave the 1 change material is maintained in a steady water column and to sink throu h a regenerstate of suspension in the hard water curating solution in preparation or fresh adrentcontinuously. mission to the hard water column.

A process of water softening by means In witness whereof, r hereunto subscribe $0 of base exchange material in the granular my name this 15th day of September, A. D.

1 condition which consists in causing the hard 1925. r J

water to be softened to flow upwardly in a column in acontainer at a linear velocity ERIC BERKELEY HIGGINS. 

